Poly(ester-carbonate) copolymers, articles formed therefrom, and methods of manufacture

ABSTRACT

A poly(ester-carbonate) copolymer comprises carbonate units of the formula (I); and ester units of the formula (II) wherein: T is a C 2-20  alkylene, a C 6-20  cycloalkylene, or a C 6-20  arylene; and R1 and J are each independently a bisphenol A divalent group and a phthalimidine divalent group, provided that the phthalimidine divalent group is present in an amount of 40 to 50 mol % based on the total moles of the bisphenol A divalent groups and the C  1/2  divalent group, and the ester units are present in an amount of 40 to 60 mol % based on the sum of the moles of the carbonate units and the ester units; and wherein the poly(ester-carbonate) copolymer has a weight average molecular weight of 18,000 to 24,000 Daltons; and the composition has a Tg of 210 to 235° C. and a melt viscosity of less than 1050 Pa-s at 644 sec −1  and 350° C.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage application of PCT/IB2017/052501,filed Apr. 28, 2017, which claims the benefit of U.S. ProvisionalApplication No. 62/328,879, filed Apr. 28, 2016, both of which areincorporated by reference in their entirety herein.

BACKGROUND

This disclosure is directed to poly(ester-carbonate) copolymers,thermoplastic compositions including the poly(ester-carbonate)copolymers, articles formed therefrom, and their methods of manufacture,and in particular high flow, high heat poly(ester-carbonate) copolymersand compositions and articles formed therefrom.

Polycarbonates are useful in the manufacture of articles and componentsfor a wide range of applications, from automotive parts to electronicappliances. Because of their broad use, particularly in automotive,lighting and consumer electronics industries, it is desirable to providepolycarbonates having high heat capacities and good surface propertiessuch as the ability to be metalized. In addition, many of theseapplications require thin wall thicknesses or high flow lengths.Accordingly, it is also desirable for these compositions to have goodmelt flow lengths (low melt viscosities) and good melt stability (lackof melt viscosity shift) at the processing conditions.

SUMMARY

A poly(ester-carbonate) copolymer comprises: carbonate units of theformula

andester units of the formula

wherein:

T is a C₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀ arylene; and

R¹ and J are each independently

-   -   (a) a bisphenol A divalent group of the formula

-   -    or    -   (b) a phthalimidine divalent group of the formula

-   -   -   wherein            -   R^(a) and R^(b) are each independently a C₁₋₁₂ alkyl,                C₂₋₁₂ alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy,            -   each R³ is independently a C₁₋₆ alkyl,            -   R⁴ is hydrogen, C₁₋₆ alkyl, or phenyl optionally                substituted with 1 to 5 C₁₋₆ alkyl groups, preferably                wherein R⁴ is hydrogen, methyl, or phenyl,            -   p, q, and j are each independently 0 to 4,

    -   provided that        -   the phthalimidine group (b) is present in an amount of 40            mol % to 50 mol % based on the total moles of the bisphenol            A divalent groups (a) and the phthalimidine groups (b);        -   the ester units are present in an amount of 40 mol % to 60            mol % based on the sum of the moles of the carbonate units            and the ester units; and            wherein

the poly(ester-carbonate) copolymer has a weight average molecularweight of 18,000 Daltons to 24,000 Daltons, as measured by gelpermeation chromatography, using a crosslinked styrene-divinylbenzenecolumn and calibrated to bisphenol A homopolycarbonate references; and

a sample of the composition has

-   -   a glass transition temperature of 210° C. to 235° C. as        determined by differential scanning calorimetry (DSC) as per        ASTM D3418 with a 20° C./min heating rate; and    -   a melt viscosity of less than 1050 Pa·s at 644 sec⁻¹ and 350°        C., determined according to ISO11443.

A method for the manufacture of the poly(ester-carbonate) copolymercomprises: providing a slurry comprising water, a water-immiscibleorganic solvent, a phase transfer catalyst, and bisphenol A; co-feedingto the slurry a solution comprising aqueous NaOH or aqueous KOH, anaromatic dicarboxylic halide of the formula

wherein T is a C₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀arylene, and a dihydroxy compound of the formula

wherein R^(a) and R^(b) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy, each R³ is independently aC₁₋₆ alkyl, R⁴ is hydrogen, C₁₋₆ alkyl, or phenyl optionally substitutedwith 1 to 5 C₁₋₆ alkyl groups, preferably wherein R⁴ is hydrogen,methyl, or phenyl, p, q, and j are each independently 0 to 4; to providea polyester oligomer; and reacting the polyester oligomer with acarbonate source to provide the poly(ester-carbonate).

In another embodiment, disclosed is a thermoplastic compositioncomprising the poly(ester-carbonate).

In yet another embodiment, an article comprises the above-describedpoly(ester-carbonate) copolymer or thermoplastic composition.

In still another embodiment, a method of manufacture of an articlecomprises molding, extruding, or shaping the above-describedpoly(ester-carbonate) copolymer or thermoplastic composition into anarticle.

The above described and other features are exemplified by the followingdrawings, detailed description, examples, and claims.

DETAILED DESCRIPTION

The inventors hereof have discovered that in poly(ester-carbonate)copolymers formed from high heat monomers, careful selection of monomersin the ester units and the carbonate units, as well as the carefulselection of relative percentage of the high heat monomer units and theester units, and the weight average molecular weight of thepoly(ester-carbonate) copolymers, can provide copolymers with high heatresistance, good surface properties, and desirable melt viscosity. Thediscovery allows the manufacture of compositions suitable for use inthin wall high flow articles with high thermal resistance and improvedadhesion to metal.

Moreover, the poly(ester-carbonate) copolymers can be miscible withpolycarbonate homopolymers or other poly(ester-carbonate) copolymers.Thus blends having low haze can be provided, which offers a flexibilityto further tune the thermal resistance and other properties of thepoly(ester-carbonate) copolymers.

The poly(ester-carbonate) copolymers, also known aspolyester-polycarbonates, comprise carbonate units of formula (1)

and ester units of formula (2)

wherein the variables T, R¹ and J are further described below.

In formula (2), T is a divalent group derived from a dicarboxylic acid(including a reactive derivative thereof), and can be, for example, aC₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀ arylene. Preferably, Tis a C₆₋₂₀ divalent aromatic group such as a divalent isophthaloylgroup, a divalent terephthaloyl group, or a combination thereof.Aromatic dicarboxylic acids that can be used to prepare the polyesterunits include isophthalic or terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, or a combination comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids include terephthalic acid, isophthalic acid,naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, or acombination comprising at least one of the foregoing acids. A specificdicarboxylic acid comprises a combination of isophthalic acid andterephthalic acid wherein the weight ratio of isophthalic acid toterephthalic acid is 91:9 to 2:98. Aliphatic dicarboxylic acid that canbe used to prepare the polyester units include a linear C₆₋₂₀ aliphaticdicarboxylic acid (which includes a reactive derivative thereof),preferably a linear C₆-C₁₂ aliphatic dicarboxylic acid (which includes areactive derivative thereof). Specific dicarboxylic acids includen-hexanedioic acid (adipic acid), n-decanedioic acid (sebacic acid), andalpha, omega-C₁₂ dicarboxylic acids such as dodecanedioic acid (DDDA).

Further in formulas (1) and (2), R¹ and J are each independently (a) abisphenol A divalent group or (b) a phthalimidine divalent group derivedfrom a specific high heat monomer as further described below. In anembodiment, R¹ and J each independently consist essentially, or consistof, (a) a bisphenol A divalent group and (b) a phthalimidine or higherdivalent group derived from a specific high heat monomer as furtherdescribed below

As is known in the art, the bisphenol A divalent group is of the formula

All or a portion of the R¹ groups can be the bisphenol A divalentgroups, provided that at least a portion of the J groups are thephthalimidine divalent group; or all portion of the J groups can be thebisphenol A divalent groups, provided that at least a portion of the R¹groups are the phthalimidine divalent group.

The phthalimidine divalent group (b) is of formula (3)

wherein R^(a) and R^(b) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy, preferably a C₁₋₃ alkyl, eachR³ is independently a C₁₋₆ alkyl, R⁴ is hydrogen, C₁₋₆ or C₂₋₆ alkyl orphenyl optionally substituted with 1 to 5 C₁₋₆ alkyl groups, and p, q,and j are each independently 0 to 4, preferably 0 to 1. For example, thephthalimidine divalent group can be of formula (3a)

wherein R⁵ is hydrogen, phenyl optionally substituted with up to fiveC₁₋₆ alkyl groups, or C₁₋₄ alkyl, preferably C₂₋₄ alkyl. In anembodiment, R⁵ is hydrogen, methyl, or phenyl, most preferably phenyl.When R⁵ is phenyl, R¹ and J can be derived from2-phenyl-3,3′-bis(4-hydroxy phenyl)phthalimidine (also known as3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one, or N-phenylphenolphthalein bisphenol or “PPPBP”). A combination of differentphthalimidine divalent groups can be used.

In an embodiment, at least one phthalimidine divalent group (b) ispresent in the ester groups of the poly(ester-carbonate) copolymer. Insome embodiments, R¹ and J are each independently the bisphenol Adivalent group or the phthalimidine divalent group (b), and at least aportion of the J groups are the phthalimidine group. For example,greater than 20 mol % and less than 35 mol % of the J groups can be thephthalimidine group based on the total moles of the J groups.

In an embodiment, the poly(ester-carbonate) copolymer comprisesphthalimidine divalent groups (b), and the mole percent of phthalimidinedivalent groups (Mol % PPP), the molar percent of the ester units (Mol %Ester), and the weight average molecular weight of poly(ester-carbonate)copolymers (Mw) are selected according to the formula:Tg=127.1+(0.94375×Mol % PPP)+(0.3875×Mol % Ester)+(0.00164968×Mw),wherein Tg is a glass transition temperature of 210° C. to 235° C. asdetermined by differential scanning calorimetry (DSC) as per ASTM D3418with a 20° C./min heating rate. The Mw and Mol % Ester and % PPP arealso adjusted such that the melt viscosity is less than 1,050 Pa·s at644 sec-1 at 350° C. or less than 1,000 Pa·s at 644 sec-1 at 350° C.,wherein the melt viscosity is determined in accordance with ISO 11443.

The poly(ester-carbonate) copolymer can comprisephthalimidine-carbonate-phthalimidine linkages of formula (20)

in an amount of greater than 15 mol % and less than 50 mol % based onthe total moles of the carbonate linkages as determined by carbon-13nuclear magnetic resonance spectroscopy (¹³C NMR). Thepoly(ester-carbonate) copolymer can also comprise linkages of formula(20) in an amount of greater than 15 mol % and less than 40 mol % basedon the total moles of the carbonate linkages as determined by ¹³C NMR.

In another embodiment, the poly(ester-carbonate) copolymer can comprisephthalimidine-carbonate-bisphenol A linkages of formula (21)

in an amount of greater than 20 mol % and less than 60 mol % based onthe total moles of the carbonate linkages as determined by ¹³C NMR. Thepoly(ester-carbonate) copolymer can also comprise linkages of formula(21) in an amount of greater than 30 mol % and less than 50 mol % basedon the total moles of the carbonate linkages as determined by ¹³C NMR.

The phthalimidine divalent group (b) is present in an amount of 40 mol %to 50 mol %, based on the total moles of the bisphenol A divalent groupsand the phthalimidine divalent group.

The ester units of the poly(ester-carbonate) copolymer are present in anamount of 40 mol % to 60 mol % based on the sum of the moles of thecarbonate units and the ester units in the poly(ester-carbonate)copolymer.

The poly(ester-carbonate) copolymers can have a weight average molecularweight of 18,000 to 24,000 Daltons, as measured by gel permeationchromatography (GPC), using a crosslinked styrene-divinylbenzene columnand calibrated to bisphenol A homopolycarbonate references. GPC samplesare prepared at a concentration of 1 mg per ml, and are eluted at a flowrate of 1.5 ml per minute.

The poly(ester-carbonate) copolymers can have flow properties useful forthe manufacture of thin articles. Melt volume flow rate (oftenabbreviated MVR) measures the rate of extrusion of a thermoplasticthrough an orifice at a prescribed temperature and load.Poly(ester-carbonate) copolymers useful for the formation of thinarticles can have an MVR of 10 to 30, preferably 15 to 25 cm³/10minutes, measured at 337° C. under a load of 6.7 kg in accordance withASTM D1238-04.

The poly(ester-carbonate) copolymers at a given temperature such as 350°C., can have a melt viscosity of less than 1050 Pa·s at 644 sec⁻¹ orless than 1000 Pa·s at 644 sec⁻¹ and can have a shift in melt viscosityof less than 25% at that temperature over 30 min under a nitrogenatmosphere as measured in a small amplitude oscillatory time sweeprheology at a fixed angular frequency of 10 radians/sec, where the meltviscosity is determined in accordance with ISO11443.

The poly(ester-carbonate) copolymers can have a high glass transitiontemperature (Tg). The Tg of the poly(ester-carbonate) copolymers can be210 to 235° C. or 220 to 235° C., determined by differential scanningcalorimetry (DSC) as per ASTM D3418 with a 20° C./min heating rate.

The poly(ester-carbonate) copolymers can have high heat resistance. Theheat deflection temperature (HDT) of the poly(ester-carbonate)copolymers is 175 to 225° C., preferably 200 to 225° C., measured on a3.18 mm bar at 0.45 MPa according to ASTM D648.

The poly(ester-carbonate) copolymers can have high Vicat softeningtemperature. In an embodiment, the poly(ester-carbonate) copolymers havea Vicat B120 of 200 to 225° C., preferably 220 to 225° C., measuredaccording to ISO 306.

The poly(ester-carbonate) copolymers can have excellent metallizationproperties. In an embodiment, a metalized sample of thepoly(ester-carbonate) copolymer has a defect onset temperature that iswithin 20 degrees Celsius of the heat deflection temperature of thepoly(ester-carbonate) copolymer where the HDT is measured flat on a80×10×4 mm bar with a 64 mm span at 0.45 MPa according to ISO 75/Bf. Inanother embodiment, a metalized sample of the poly(ester-carbonate)copolymer has a defect onset temperature that is within 10 degreesCelsius of the heat deflection temperature of the poly(ester-carbonate)copolymer where the HDT is measured flat on a 80×10×4 mm bar with a 64mm span at 0.45 MPa according to ISO 75/Bf.

The poly(ester-carbonate) copolymers can have a defect onset temperatureof 200° C. or greater. In an embodiment, the poly(ester-carbonate)copolymers have a defect onset temperature of 200° C. to 220° C.

The poly(ester-carbonate) copolymers can have a visual transmission(Tvis) of 80% to 90% measured on HAZE-GUARD plus from BYK-Gardnerinstruments.

The poly(ester-carbonate) copolymers can have a yellowness index of lessthan 18 determined according to ISO 306.

The poly(ester-carbonate) copolymers can further have a Notched IzodImpact of 5 to 10 KJ/m², determined in accordance with ISO 180 under aload of 5.5 J at 23° C. on a sample of 3 mm thickness.

Also disclosed are thermoplastic compositions comprising thepoly(ester-carbonate). In addition to the poly(ester-carbonate), thethermoplastic compositions can further comprise a polycarbonatehomopolymer such as a bisphenol A homopolycarbonate, a copolycarbonate,a second poly(ester-carbonate) that is different from thepoly(ester-carbonate) copolymer described above, or a combinationcomprising at least one of the foregoing. The poly(ester-carbonate)copolymer can be present in an amount of 10 wt % to 90 wt % and thepolycarbonate homopolymer, the copolycarbonate, the secondpoly(ester-carbonate) different from the poly(ester-carbonate)copolymer, or a combination thereof can be present in an amount of 1 wt% to 90 wt %, each based on the total weight of the thermoplasticcomposition.

The homopolycarbonate and the copolycarbonate can comprise carbonateunits of formula (12)

wherein at least 60 percent of the total number of R¹ groups arearomatic, or each R¹ contains at least one C₆₋₃₀ aromatic group.Specifically, each R¹ can be derived from a dihydroxy compound such asan aromatic dihydroxy compound of formula (13) or a bisphenol of formula(14).

In formula (13), each R^(h) is independently a halogen atom, for examplebromine, a C₁₋₁₀ hydrocarbyl group such as a C₁₋₁₀ alkyl, ahalogen-substituted C₁₋₁₀ alkyl, a C₆₋₁₀ aryl, or a halogen-substitutedC₆₋₁₀ aryl, and n is 0 to 4. In formula (14), R^(a) and R^(b) are eachindependently a halogen, C₁₋₁₂ alkoxy, or C₁₋₁₂ alkyl, and p and q areeach independently integers of 0 to 4, such that when p or q is lessthan 4, the valence of each carbon of the ring is filled by hydrogen. Inan embodiment, p and q are each 0, or p and q are each 1, and R^(a) andR^(b) are each a C₁₋₃ alkyl group, preferably methyl, disposed meta tothe hydroxy group on each arylene group. X^(a) in formula (14) is abridging group connecting the two hydroxy-substituted aromatic groups,where the bridging group and the hydroxy substituent of each C₆ arylenegroup are disposed ortho, meta, or para (preferably para) to each otheron the C₆ arylene group, for example, a single bond, —O—, —S—, —S(O)—,—S(O)₂—, —C(O)—, or a C₁₋₁₈ organic group, which can be cyclic oracyclic, aromatic or non-aromatic, and can further comprise heteroatomssuch as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. Forexample, X^(a) can be a substituted or unsubstituted C₃₋₁₈cycloalkylidene; a C₁₋₂₅ alkylidene of the formula —C(R^(c))(R^(d))—wherein R^(c) and R^(d) are each independently hydrogen, C₁₋₁₂ alkyl,C₁₋₁₂ cycloalkyl, C₇₋₁₂ arylalkyl, C₁₋₁₂ heteroalkyl, or cyclic C₇₋₁₂heteroarylalkyl; or a group of the formula —C(═R^(e))— wherein R^(e) isa divalent C₁₋₁₂ hydrocarbon group. Some illustrative examples ofdihydroxy compounds that can be used are described, for example, in WO2013/175448 A1, US 2014/0295363, and WO 2014/072923. Specific dihydroxycompounds include resorcinol, BPA, the bisphenols of formula (8),specifically of formula (8a), more specifically of formula (8b) (PPPBP)

wherein R³, R⁴, R⁵, R_(a), R_(b), j, p, and q are as defined for formula(3) and (3a), or the bisphenols of formula (9)-(11), such as1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, and BP-TMC:

wherein R^(c) and R^(d) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy, each R⁶ is independently C₁₋₃alkyl or phenyl, preferably methyl, X^(a) is a C₆₋₁₂ polycyclic aryl,C₃₋₁₈ mono- or polycycloalkylene, a C₃₋₁₈ mono- or polycycloalkylidene,or a -(Q¹)_(x)-G-(Q²)_(y)- group, wherein Q¹ and Q² are eachindependently a C₁₋₃ alkylene, G is a C₃₋₁₀ cycloalkylene, x is 0 or 1,y 1, and m and n are each independently 0 to 4. In formula (6), eachbond to the polymer functional group is located a position para to thegroup X^(a). A combination of different divalent groups (b) can be used.In an embodiment, at least one divalent group (b) is present in theester groups of the poly(ester-carbonate) copolymer.

Exemplary bisphenols of formula (11) include the following:

wherein R^(c), R^(d), R², R³, g, m, and n are the same as defined hereinfor formulas (9)-(11). In a specific embodiment the C₁₆ or higherdivalent group is derived from1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, or a combination thereof.

In an embodiment, the polycarbonate is a BPA homopolymer. In anotherembodiment, the polycarbonate is a copolycarbonate comprising bisphenolA carbonate units and additional carbonate units derived from a highheat monomer. Examples of such copolycarbonates include copolycarbonatescomprising bisphenol A carbonate units and2-phenyl-3,3′-bis(4-hydroxyphenyl) phthalimidine carbonate units (aBPA-PPPBP copolymer, commercially available under the trade name XHTfrom SABIC) and a copolymer comprising bisphenol A carbonate units and1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane bisphenol carbonateunits.

The second poly(ester-carbonate) different from thepoly(ester-carbonate) copolymer described above, can further contain, inaddition to recurring carbonate units (12), repeating ester units offormula (15)

wherein T² is a divalent group derived from a dicarboxylic acid (whichincludes a reactive derivative thereof), and can be, for example, aC₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀ arylene. Aliphaticdicarboxylic acids that can be used include C₆₋₂₀ aliphatic dicarboxylicacids (which includes the terminal carboxyl groups), preferably linearC₈₋₁₂ aliphatic dicarboxylic acid such as decanedioic acid (sebacicacid); and alpha, omega-C₁₂ dicarboxylic acids such as dodecanedioicacid (DDDA). Aromatic dicarboxylic acids that can be used includeterephthalic acid, isophthalic acid, naphthalene dicarboxylic acid,1,6-cyclohexane dicarboxylic acid, or a combination comprising at leastone of the foregoing acids. A combination of isophthalic acid andterephthalic acid wherein the weight ratio of isophthalic acid toterephthalic acid is 91:9 to 2:98 can be used.

Further in formula (15), J² is a divalent group derived from a dihydroxycompound (which includes a reactive derivative thereof), and can be, forexample, a C₂₋₁₀ alkylene, a C₆₋₂₀ cycloalkylene a C₆₋₂₀ arylene, or apolyoxyalkylene group in which the alkylene groups contain 2 to 6 carbonatoms, preferably, 2, 3, or 4 carbon atoms. Specific dihydroxy compoundsfor use in the second poly(ester-carbonate) include an C₁₋₈ aliphaticdiol such as ethane diol, n-propane diol, i-propane diol, 1,4-butanediol, 1,6-cyclohexane diol, 1,6-hydroxymethylcyclohexane; an aromaticdihydroxy compounds of formula (13) such as resorcinol; or a bisphenolof formula (14), such as bisphenol A.

Second poly(ester-carbonate)s containing a combination of different T²or J² groups can be used. The polyester units can be branched or linear.Specific ester units include ethylene terephthalate units, n-propyleneterephthalate units, n-butylene terephthalate units, ester units derivedfrom isophthalic acid, terephthalic acid, and resorcinol (ITR esterunits), and ester units derived from sebacic acid and bisphenol A. Themolar ratio of ester units to carbonate units in the secondpoly(ester-carbonate)s can vary broadly, for example 1:99 to 99:1,preferably, 10:90 to 90:10, more preferably, 25:75 to 75:25, or from2:98 to 15:85. In some embodiments the molar ratio of ester units tocarbonate units in the second poly(ester-carbonate)s can vary from 1:99to 30:70, preferably 2:98 to 25:75, more preferably 3:97 to 20:80, orfrom 5:95 to 15:85.

The poly(ester-carbonate) copolymers, in particular the PPPBP/BPApoly(ester-carbonate)s can be prepared by methods known in the art, forexample as described in U.S. Pat. No. 8,487,065, such as in Example 7.In particular, the poly(ester-carbonate)s can be manufactured byinterfacial polymerization. Although the reaction conditions forinterfacial polymerization can vary, an exemplary process generallyinvolves dissolving or dispersing the dihydroxy compound and diacidcompound in aqueous NaOH or KOH, adding the resulting mixture to awater-immiscible solvent, and contacting the reactants with a carbonateprecursor in the presence of a catalyst such as, for example, a tertiaryamine or a phase transfer catalyst, under controlled pH conditions,e.g., 8 to 10. Rather than using the dicarboxylic acid or diol directly,the reactive derivatives of the diacid or diol, such as thecorresponding acid halides, in particular the acid dichlorides and theacid dibromides can be used. Thus, for example instead of usingisophthalic acid, terephthalic acid, or a combination comprising atleast one of the foregoing acids, isophthaloyl dichloride, terephthaloyldichloride, or a combination comprising at least one of the foregoingdichlorides can be used.

The water-immiscible solvent can be, for example, methylene chloride,1,2-dichloroethane, chlorobenzene, toluene, and the like. Exemplarycarbonate precursors include a carbonyl halide such as carbonyl bromideor carbonyl chloride (phosgene) a bishaloformate of a dihydroxy compound(e.g., the bischloroformate of bisphenol A, hydroquinone ethyleneglycol, neopentyl glycol, or the like), and diaryl carbonates.Combinations comprising at least one of the foregoing types of carbonateprecursors can also be used.

The diaryl carbonate ester can be diphenyl carbonate, or an activateddiphenyl carbonate having electron-withdrawing substituents on the eacharyl, such as bis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate,bis(4-chlorophenyl)carbonate, bis(methyl salicylate)carbonate,bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphenyl) carboxylate,bis(4-acetylphenyl) carboxylate, or a combination comprising at leastone of the foregoing.

In some embodiments, the poly(ester-carbonate) copolymers are preparedby providing a slurry of bisphenol A and the phase transfer catalyst ina mixture of the water and water-immiscible organic solvent; andco-feeding the acid halide of the dicarboxylic acid, the dihydroxycompound of formula (8), (8a), or (8b) in a solution of caustic toprovide polyester oligomers, which are then reacted with the carbonateprecursor. In particular, the process includes combining bisphenol A ina water-immiscible organic solvent such as methylene chloride, and waterin the presence of an endcapping agent as described below and a phasetransfer catalyst such as triethylamine in a reactor. A caustic such asNaOH or KOH is added together with a solution of the dihydroxy compoundof formula (8), (8a), or (8b) in caustic (e.g., aqueous NaOH or KOH),while a mixture of molten diacid halide derived from the correspondingdicarboxylic acid of T (e.g., isophthaloyl and terephthaloyl chloride)are concurrently added. Aqueous caustic can be added as needed toprevent the pH from decreasing below 8-9 in the reactor. After theadditions are complete, a carbonyl source such as phosgene is added withsufficient aqueous caustic to maintain a pH of 8-9 in the reactor. Theprogress of the reaction is monitored (e.g., by GPC), and additionalcarbonyl source added as needed until the reaction has proceeded to thedesired degree of completion. The resulting poly(ester-carbonate)copolymers can be isolated and purified by methods known in the art. Forexample, the poly(ester-carbonate) copolymers, can by purified on acentrifuge train where the brine phase is separated and the polymersolution in methylene chloride is extracted with aqueous HCl and thenwashed with deionized water until titratable chlorides are at a desiredlevel, for example less than 50, or less than 5 ppm. The methylenechloride solution can then be steam precipitated and the polymer dried,for example under hot nitrogen, until the desired volatile levels areobtained, for example less than 1 wt. % or less than 0.4 wt %.

As described above, an end-capping agent (also referred to as a chainstopper agent or chain terminating agent) can be included duringpolymerization to provide end groups, for example monocyclic phenolssuch as phenol, p-cyanophenol, and C₁₋₂₂ alkyl-substituted phenols suchas p-cumyl-phenol, resorcinol monobenzoate, and p- and tertiary-butylphenol, monoethers of diphenols, such as p-methoxyphenol, monoesters ofdiphenols such as resorcinol monobenzoate, functionalized chlorides ofaliphatic monocarboxylic acids such as acryloyl chloride and methacryoylchloride, and mono-chloroformates such as phenyl chloroformate,alkyl-substituted phenyl chloroformates, p-cumyl phenyl chloroformate,and toluene chloroformate. Combinations of different end groups can beused. Branched polymers can be prepared by adding a branching agentduring polymerization, for example trimellitic acid, trimelliticanhydride, trimellitic trichloride, tris-p-hydroxyphenylethane,isatin-bis-phenol, tris-phenol TC(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA(4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, andbenzophenone tetracarboxylic acid. The branching agents can be added ata level of 0.05 to 2.0 wt %.

The thermoplastic compositions containing the poly(ester-carbonate)copolymers can include various additives ordinarily incorporated intopolymer compositions of this type, with the proviso that the additive(s)are selected so as to not significantly adversely affect the desiredproperties of the thermoplastic composition, in particular melt flow,thermal, and surface properties. Such additives can be mixed at asuitable time during the mixing of the components for forming thecomposition. Additives include fillers, reinforcing agents,antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV)light stabilizers, plasticizers, lubricants, mold release agents,antistatic agents, colorants such as such as titanium dioxide, carbonblack, and organic dyes, surface effect additives, radiationstabilizers, flame retardants, and anti-drip agents. A combination ofadditives can be used, for example a combination of a heat stabilizer,mold release agent, and ultraviolet light stabilizer. In general, theadditives are used in the amounts generally known to be effective. Forexample, the total amount of the additives (other than any impactmodifier, filler, or reinforcing agents) can be 0.01 to 5 wt %, based onthe total weight of the thermoplastic composition.

The thermoplastic compositions can be manufactured by various methodsknown in the art. For example, powdered poly(ester-carbonate), and otheroptional components are first blended, optionally with any fillers, in ahigh speed mixer or by hand mixing. The blend is then fed into thethroat of a twin-screw extruder via a hopper. Alternatively, at leastone of the components can be incorporated into the composition byfeeding it directly into the extruder at the throat or downstreamthrough a sidestuffer, or by being compounded into a masterbatch with adesired polymer and fed into the extruder. The extruder is generallyoperated at a temperature higher than that necessary to cause thecomposition to flow. The extrudate can be immediately quenched in awater bath and pelletized. The pellets so prepared can be one-fourthinch long or less as desired. Such pellets can be used for subsequentmolding, shaping, or forming.

The thermoplastic composition has a haze of less than 15% and atransmission greater than 75%, each measured using the color spaceCIE1931 (Illuminant C and a 2° observer) at a 3.2 mm thickness.

The thermoplastic composition has an MVR of 5 to 30, preferably 10 to30, more preferably 18 to 28 cm³/10 minutes, measured at 337° C. under aload of 6.7 kg in accordance with ASTM D1238-04.

The thermoplastic composition at a given temperature such as 350° C. or370° C., has a melt viscosity of less than 1050 Pa·s at 644 sec⁻¹ andhas shift in melt viscosity of less than 25% at that temperature over 30min under a nitrogen atmosphere as measured in a small amplitudeoscillatory time sweep rheology at a fixed angular frequency of 10radians/sec, where the melt viscosity is determined in accordance withISO11443.

The thermoplastic composition has a heat deflection temperature (HDT) of195 to 225° C., measured flat on a 80×10×4 mm bar with a 64 mm span at0.45 MPa according to ISO 75/Bf.

The thermoplastic composition has excellent metallization properties. Inan embodiment, a metalized sample of the thermoplastic composition has adefect onset temperature that is within 20 degrees Celsius, preferablywithin 10 degrees Celsius of the heat deflection temperature of thepoly(ester-carbonate) copolymer where the HDT is measured flat on a80×10×4 mm bar with a 64 mm span at 0.45 MPa according to ISO 75/Bf.

Shaped, formed, or molded articles comprising the poly(ester-carbonate)copolymers or the thermoplastic compositions are also provided. Thecopolymers and compositions can be molded into useful shaped articles bya variety of methods, such as injection molding, extrusion, rotationalmolding, blow molding, and thermoforming. Some example of articlesinclude computer and business machine housings such as housings formonitors, handheld electronic device housings such as housings for cellphones, electrical connectors, and components of lighting fixtures,ornaments, home appliances, roofs, greenhouses, sun rooms, swimming poolenclosures, and the like. Additional exemplary articles include a plug,a plug housing, a switch, an electrical conductor, a connector, anelectric board, a lamp holder, a lamp cover, a lamp bezel, a reflector,a signal indicator, glazing, a lens, a lens holder, a waveguide element,a collimator, a light emitting diode, a diffuser sheet, a safety pane, afilm, a film laminate, a safety goggle, and a visor.

The article comprising the poly(ester-carbonate) copolymers or thethermoplastic compositions can be a metallized article. The metallizedarticle comprises, for example, a substrate comprising thepoly(ester-carbonate) copolymers, the polycarbonate blends, orthermoplastic compositions, with a metal layer disposed on the at leastone side of the substrate.

The substrate can be for example, a film. The substrate can be made bymolding the poly(ester-carbonate) copolymers or the thermoplasticcompositions. The molding methods are not particularly limited, andvarious known molding methods can be listed, for example, injectionmolding, gas assist injection molding, vacuum molding, extrusion,compression molding, calendaring, rotary molding, etc. Of these, moldingis usually carried out by injection molding.

The metal layer can be disposed onto the surface of the substrate withthe aid of electrocoating deposition, physical vapor deposition, orchemical vapor deposition or a suitable combination of these methods.Sputtering processes can also be used. The metal layer resulting fromthe metallizing process (e.g., by vapor deposition) can be 0.001 to 50micrometers (μm) thick.

A base coat can be present between the substrate and the metal layer.However, it is advantageous to form the metal layer directly on thesubstrate surface without forming an undercoat. The surfaces of thesubstrate are smooth and good gloss can be obtained even by direct metalvapor deposition without treating the substrate with a primer. Moreover,the release properties of the molded substrate during injection moldingare good. Accordingly, the surface properties of the molded substrateare superior without replication of mold unevenness.

Chrome, nickel, aluminum, etc. can be listed as examples of vaporizingmetals. Aluminum vapor deposition is used in one embodiment as metalvapor deposition. The surface of the molded substrate can be treatedwith plasma, cleaned, or degreased before vapor deposition in order toincrease adhesion.

The metallized article can have a protective layer disposed on the metallayer. “Protective layer” refers for example, to a layer which is madeof a binder or a high molecular weight polymer and formed on theoutermost (e.g., the UV blocking) layer, so as to exert the effects ofpreventing marring and improving mechanical properties of the multilayerarticle. The protective layer can be clear or pigmented and beformulated, for example, with nitrocellulose or synthetic polymersconfigured to quickly dry by evaporation without chemical reaction withthe layer on which they are disposed, providing a solid protectivelayer. The protective coating material can further be thinned withalcohols. In certain applications, the thickness of the protective layeris minimized. The thickness of the protective layer can be, for example,0.2 μm or less.

The metallized articles can have little mold shrinkage, have goodsurface gloss even when metal layers are directly vapor deposited, andthe vapor deposited surfaces do not become cloudy or have rainbowpatterns even on heating of the vapor deposited surface. In particular,the metallized article can have no surface defects visible to the eye.

Illustratively, the metallized article has a metallized surface, whereinthe surface can exhibit a gloss of greater than 95 units, or greaterthan 170 units, measured at 20 degrees using a trigloss meter. Themetallized surface can also retain 85%, 88%, 90%, 95% or more of itsgloss after heat aging at 150° C. for 1 hour, measured at 20 degreesusing a micro trigloss meter. A base coat (undercoat) can be presentbetween the article and the metallized surface, or a surface of thearticle can be directly metallized.

Metallized articles have applications in optical reflectors and can beused for automotive headlamps, headlight extensions, and headlampreflectors, for indoor illumination, for vehicle interior illuminationand for the like.

EXAMPLES

The chemicals used in the Examples are described in Table 1.

TABLE 1 Component Chemical description Source BPA Bisphenol A PPPBP orPPP 3,3-bis(4-hydroxyphenyl)-2- SABIC phenylisoindolin-1-one orcarbonate or ester units derived from the monomer PEI PolyetherimideSABIC PES Polyethersulfone, BASF ULTRASON E2010 PES Hindered phenolOctadecyl-3-(3,5-di-tert-butyl-4- BASF hydroxyphenyl) propionatePhosphite stabilizer Tris(di-t-butylphenyl)phosphite BASF LubricantPentaerythritol tristearateBlending, Extrusion, and Molding Conditions

All the formulations were dry blended with the appropriate additives, ifany, and mixed in a paint shaker. The blends were extruded on 26 mmtwin-screw (T8) extruder with barrel temperatures set points ramped from540 to 640° F. (feed to die throat), vacuum venting and a screw speed of300 rpms. The extrudate was cooled in a water bath and then chopped intopellets for testing and molding. It will be recognized by one skilled inthe art that the method is not limited to these processing steps orprocessing equipment.

Molding of ASTM Test Parts

A 180-ton injection molding machine with a 5.25 oz. barrel was used tomold ASTM test samples. The polymer blends were molded at 630 to 640° F.after drying for 4 hours and at 250° F. with a 35 sec cycle time. Anoil-thermolator was used to heat cavity and core sides of the mold to asurface temperature of 250° F.

Testing Methods.

Weight average molecular weight (Mw) determinations were performed usingGPC using a cross linked styrene-divinyl benzene column, at a sampleconcentration of 1 milligram per milliliter, and as calibrated withbisphenol A homopolycarbonate standards. Samples were eluted at a flowrate of 1.0 ml/min with methylene chloride as the eluent.

Metallization was performed on molded parts from a film gate injectionset-up having dimensions 60 mm×60 mm and a thickness of either 3 mm or1.5 mm using the physical vapor deposition (PVD) process. The processdeposited a 100 to 150 nm thick aluminum layer onto one side of themolded part under vacuum, followed by a protective plasma-depositedsiloxane hard-coat of 50 nm.

“Defect onset temperature” (DOT) was determined as the highesttemperature at which no visual defects appeared on a metallized sampleafter 1 hour of heat aging in an air circulating oven, exposing allsides of the sample (symmetric heating). The thermal treatment of themetallized samples was carried out at least 48 hours after the partswere metallized.

The reflection data of the metallized articles and the heat treatedmetallized articles was acquired on an X-rite 1-7 spectrophotometeraccording to ASTM D1003-00 using a 25 mm aperture under D65 illuminationin specular reflection mode and 10 degrees observer.

Visual defects were measure by eye with a trained operator and by anincrease in L*. There are two common modes of failure during thermaltreatment of the metallized parts. The parts can become hazy with theresult that these parts exhibit an increase in diffuse reflection, whichcan be measured as an increase in L* when the parts are measured inreflection mode under specular excluded conditions. The parts can alsofail due to blistering, which may not give a significant increase indiffuse reflection but is determined by close inspection of the parts.Hence a failure is reported as “defect onset temperature” (DOT) andcaptures the temperature at which the heat treated part fails either thevisual assessment or gives a high diffuse scattering i.e. high L* inspecular reflection mode.

Melt volume rate (“MVR”) was determined in accordance with ASTM D1238-04under a load of 6.7 kg at 337° C. under a load of 5 Kg at 340 C.

Melt viscosity was determined in accordance with ISO 11443 at thetemperatures indicated.

Glass transition temperature (Tg) was determined by differentialscanning calorimetry (DSC) as per ASTM D3418 with a 20° C./min heatingrate.

Heat deflection temperature (HDT) was determined on a flat 80×10×4 mmbar with a 64 mm span according to ISO 75/Bf, at the pressuresindicated.

Heat deflection temperature was also determined on one-eighth inch 3.18mm bars per ASTM D648, at the pressures indicated.

Vicat B value was determined according to ISO 306, Method B120.

Yellowness index was determined in accordance with ASTM D1925.Transparency was described by two parameters, percent transmission andpercent haze. Percent transmission and percent haze for laboratory scalesamples were determined in accordance with ASTM D1003 using the colorspace CIE1931 (Illuminant C and a 2° observer) at a 3.2 mm thickness.

“Mole % PPP” or “PPP mol %” refers to the sum of the molar percent ofcarbonate and ester units derived from PPPBP based on the total moles ofthe carbonate and ester units. Mole % PPP can be determined by NMR.

“Mole % BPA” or “BPA mol %” refers to the sum of the molar percent ofcarbonate and ester units derived from BPA based on the total moles ofthe carbonate and ester units. Mol % BPA can be determined by NMR.

“Mole % ester” or “ester mol %” refers the molar percent of ester unitsbased on the total moles of the ester units and carbonate units. Mole %ester can be determined by NMR.

Preparation of Poly(Ester-Carbonate) Copolymer (Example Process A)

The PPPBP/BPA poly(ester-carbonate)s were prepared according thefollowing general procedure. The amounts were adjusted according to thedesired composition and Mw. To a mixture of methylene chloride (24 L),DI water (6 L), BPA (1567 g, 6.865 mol), p-cumylphenol (168.7 g, 0.7946mol), triethylamine (40 ml), and sodium gluconate (10 g) in a 75 Lreactor equipped with mechanical stirring, recirculation line with pHprobe, subsurface phosgene addition, chilled glycol condenser, causticscrubber for exit gas, and caustic solution inlet was added at 760 g/mina solution of PPPBP (2300 g, 5.73 mol) in 1488 g of 33% NaOH and 387 8 gof DI water while a mixture of molten diacid chlorides (1342 g, 6.611mol of 50/50 isophthaloyl and terephthaloyl chloride) were concurrentlyadded at 90 g/min. Aqueous caustic (33 wt %) was added as needed toprevent the pH from decreasing below 8-9 in the reactor. After theadditions were complete, the reactor was stirred for 5 min. Phosgene(1800 g, 18.1 mol) was added at 80 g/min and 33 wt % aqueous caustic wasadded as needed to maintain pH of 8-9 in the reactor. The reactor wasthen purged with nitrogen. A sample was pulled for GPC analysis. Then200 g of additional phosgene was added to the batch followed by a secondGPC analysis. If the difference between the first and second GPC wasless than 200 the batch was considered complete. If not the process wasrepeated. The batch was purified on a centrifuge train where the brinephase was separated and the polymer solution in methylene chloride wasextracted with aqueous HCl and then washed with deionized water untiltitratable chlorides were less than 5 ppm. The methylene chloridesolution was then steam precipitated and the polymer dried under hotnitrogen until volatile levels were <0.4 wt %. The preparedpoly(ester-carbonate) copolymer contained less than 100 ppm of each ofthe monomers. The ionic Cl was less than 2 ppm. The residual TEA wasless than 4 ppm.

Comparative B Process. The PPPBP/BPA poly(ester-carbonate)s wereprepared according to U.S. Pat. No. 8,487,065, Example 7. The amountswere adjusted according to the desired composition and Mw.

Examples and Comparative Examples 1-25

Various poly(ester-carbonate) copolymers were prepared according toExample Process A. The compositions and the properties of thepoly(ester-carbonate) copolymers are shown in Table 2.

TABLE 2 Melt MVR (g/cc) Visc. 337 337 350° C. HDT (ASTM) PPP Ester Mw6.7 6.7 Shift 644 s−1 Tg 1.82 GPa 0.455 GPa Examples mol % mol % Powder360 s 1800 s % Pa · s ° C. ° C. ° C.  1 46 52 19,003 17.7 18.0 1.7 731224 199 213  2 50 52 19,279 13.6 13.9 2.2 830 226 195 213  3 46 5819,056 10.6 11.1 4.7 923 225 201 215 Comp Ex 4 50 58 19,166 6.8 7.7 12.61175 230 204 220 Comp Ex 5 46 52 22,914 5.1 5.3 2.9 1336 228 202 219Comp Ex 6 50 52 23,192 5.0 5.9 17.6 1290 234 205 222 Comp Ex 7 46 5822,936 4.8 4.8 1.3 1407 231 204 221 Comp Ex 8 50 58 23,047 3.9 4.0 2.6High 235 207 224 13 48 55 17,744 22.5 23.1 2.7 681 223 205 213 Comp Ex1448 55 23,673 9.7 9.4 −2.9 1297 236 202 219 15 48 55 20,951 10.4 11.0 5.8915 227 206 218 16 48 55 20,951 10.4 11.4 9.6 984 226 202 218 17 48 5520,951 10.9 10.3 −5.5 981 229 203 218 Comp Ex18 48 55 20,951 11.0 11.00.0 1016 228 203 218 19 48 55 20,951 13.3 11.0 17.3 992 226 202 20 48 5520,951 11.8 11.9 0.8 914 226 200 217 21 42 44 22,853 220 22 46 44 19,270222 23 42 44 19,034 209 25 42 58 21,731 222 U.S. Pat. No. 8,318,891 2590 28,808 219 Ex 1 U.S. Pat. No. 8,318,891 38 31 28,276 205 Ex 2 U.S.Pat. No. 8,487,065 50 68 23163 246 Ex 7

The results indicate that preferred compositions are when the mol %PPPBP is between 40 and 50%, the mol % ester is between 40 to 60% andthe Mw of the poly(ester-carbonate) copolymer is between 18,000 and23,000 and the Tg is between 210° C. and 235° C. as calculated by theequation Tg=127.1+(0.94375 Mol % PPP)+(0.3875×Mol %Ester)+(0.00164968×Mw) and the Mw and Mol % Ester and % PPP are adjustedsuch that the melt viscosity is less than 1,050 Pa·s at 644 sec⁻¹ at350° C. or less than 1,000 Pa·s at 644 sec⁻¹ at 350° C., wherein themelt viscosity is determined in accordance with ISO 11443.

U.S. Pat. Nos. 8,318,891 and 8,487,065 discloses poly(ester-carbonate)copolymers having high glass transition temperatures, but lack teachingon providing high flow thermoplastic compositions that are suitable toprovide thin wall articles.

The composition shown in Example 1 of U.S. Pat. No. 8,318,891 has asuitable glass transition temperature of 219° C., but the compositionhas inadequate melt flow.

The composition shown in Example 2 of U.S. Pat. No. 8,318,891 has aglass transition temperature of 205° C., which is too low for certainapplications. The composition also has low melt flow properties.

The composition shown in Example 7 of U.S. Pat. No. 8,487,065 has aglass transition temperature of 246° C., which is too high for certainapplications; and because of its high Tg the composition has poor meltflow and therefore will not fill thin wall parts. The composition alsohas low melt flow.

Examples 26-43

Poly(ester-carbonate) copolymers were made according to Example ProcessA and Comparative Process B with a formulation of 46 mol % PPP, 54 mol %BPA with 52 mol % ester units. The results are shown in Tables 3-5. Thedata shows that in the poly(ester-carbonate) copolymers preparedaccording to Comparative Process B, the PPP-PPP (called BHPD-C(O)-BHPD)carbonate linkages are low as claimed in U.S. Pat. No. 8,487,065,however the PPP-ester linkages are higher as compared topoly(ester-carbonate) copolymer prepared according to Process A.

The melt stability data shows that the poly(ester-carbonate) copolymersmade by Process A give better melt stability than that of ComparativeProcess B. Poly(ester-carbonate) copolymers made from Process A have aloss in melt viscosity of less than 25% whereas those of Process C havea loss of greater than 25%.

Also even though the monomer compositions were the same, the Tgs andVicat data for the samples from Comparative Process B are significantlylower. In addition, it was found that the poly(ester-carbonate)copolymers prepared according to Process A have better color than thepoly(ester-carbonate) copolymers prepared according to Process B. Thusalthough Comparative Process B disclosed in U.S. Pat. No. 8,487,065provides poly(ester-carbonate) copolymers have better stability thanconventional PPP/BPA poly(ester-carbonate)s, the inventors havediscovered poly(ester-carbonate) copolymers having further improved meltstability and color than the compositions of U.S. Pat. No. 8,487,065.

TABLE 3 Carbonate¹ Carbonate² Ester³ (mol %) (mol %) (mol %) Mol % Mol %BPA- BPA- PPP- BPA- BPA- PPP- BPA PPP Ex # Process PPPBP Ester BPA⁴ PPP⁵PPP⁶ BPA⁴ PPP⁵ PPP⁶ BPA PPP Ex 26 A 44 50 41 41 18 21 20 9 25 25 Ex 27 A45 50 38 39 23 19 20 11 27 23 Ex 28 A 43 48 38 40 23 20 21 12 26 22 Ex29 A 42 47 36 42 22 19 22 12 26 21 Ex 30 B 45 48 96 4 0 50 2 0 10 38 Ex31 B 43 42 85 12 3 49 7 2 8 34 Ex 32 B 44 49 100 0 0 51 0 0 9 39 ¹Basedon the total moles of the carbonate linkages only ²Based on the totalmoles of the carbonate units and ester units ³Based on the total molesof the carbonate units and ester units ⁴BPA-BPA refers toBPA-carbonate-BPA linkage ⁵BPA-PPP refers to BPA-carbonate-PPP linkage⁶PPP-PPP refers to PPP-carbonate-PPP linkage

TABLE 4 Change in Tg by Mol % Mol % viscosity DSC, Vicat Ester PPP by Ex# Process 350° C. (%) ° C. 50/120 by NMR NMR Ex 33 A −18 226 220 48.944.9 Ex 34 A −16 226 221 50.0 45.2 Ex 35 A −13 224 220 49.3 45.1 Ex 36 A−16 225 221 49.3 44.8 Average −16 225 221 49 45 Stdev 2 1 1 0.4 0.2 Ex37 B −26 219 219 50.0 45.0 Ex 38 B −36 219 219 51.1 46.4 Ex 39 B −44 218217 50.0 47.0 Ex 40 B −22 219 215 49.8 45.4 Ex 41 B −26 216 215 42.741.9 Ex 42 B −19 216 216 47.9 44.4 Ex 43 B −24 216 215 49.1 44.4 Average−28 218 217 49 45 Stdev 9 1.4 1.8 2.8 1.6

TABLE 5 Mol % Mol % Ex # Process YI % T Haze Ester by NMR PPP by NMR Ex33 A 14.2 83.1 1.8 48.9 44.9 Ex 34 A 14.4 84.3 1.2 50.0 45.2 Ex 35 A15.7 84.3 1.2 49.3 45.1 Ex 36 A 14.7 84.5 0.9 49.3 44.8 Average 14.884.1 1.3 49 45 Stdev 0.7 0.6 0.4 0.4 0.2 Ex 37 B 21.7 82.9 1.0 50.0 45.0Ex 38 B na na na 51.1 46.4 Ex 39 B 21.7 82.5 1.3 50.0 47.0 Ex 40 B 18.783.2 1.2 49.8 45.4 Ex 41 B 19.0 82.9 1.2 42.7 41.9 Ex 42 B 20.0 82.9 1.047.9 44.4 Ex 43 B 18.8 83.7 0.8 49.1 44.4 Average 20.0 83.0 1.1 49 45Stdev 1.4 0.4 0.2 2.8 1.6

Examples 44 and 45

Poly(ester-carbonate) copolymers were compounded with a lubricant,phosphite stabilizer, and a hindered phenol antioxidant. Thecompositions and their properties are shown in Tables 6 and 7.

TABLE 6 Example 44 45 PPPBP Mol % 46 46 Ester Mol % 52 52 Mw, powderDaltons 23000 19300 Tg, Powder ° C. 229 225 Formulation Lubricant % 0.270.27 Phosphite Stabilizer % 0.08 0.08 Hindered phenol % 0.04 0.04 Mw,Pellets Daltons 20600 18900 Tg, Pellets ° C. 226 222 Properties TestDescription Unit 26 27 Melt Viscosity, ISO11443 855.5 686 350° C., 644s−1 Melt Viscosity, ISO11443 466.7 368.7 370° C., 644 s−1 Melt Stabilityat Viscosity Shift % −8 −4 330° C., 1800 s Melt Stability at ViscosityShift % −21 −17 350° C., 1800 s Melt Stability at Viscosity Shift % −38−29 370° C., 1800 s

TABLE 7 Example 44 45 PEI PES % Mol % PPP Mol % 46 46 Mol % Ester Mol %52 52 Mw, Powder Daltons 23000 19300 Tg, Powder ° C. 229 225 FormulationLubricant % 0.27 0.27 PHOSPHITE STABILIZER % 0.08 0.08 HINDERED PHENOLANTI-OXIDANT % 0.04 0.04 Mw, Pellets Daltons 20600 18900 Tg, Pellets °C. 226 222 Melt Flow & Viscosity MVR-ISO 340° C., 5 Kg cm³/10 min 17.815.4 12.7 Thermal Properties Unit HDT-ISO 0.45 Mpa, Flat 204 205 201HDT-ISO  1.8 Mpa, Flat 185 187 186 Metallized Article Performance DefectOnset Temperature ° C. 210 205 204 210

Examples 44 and 45 of Table 6 show that poly(ester-carbonate) copolymerscompounded into thermoplastic formulations have glass transitiontemperatures above 210° C. and melt viscosities below 1000 Pas at 350°C. and 644 s⁻¹ as well as good melt stability at 350° C. (viscosityshift less than 40%).

Table 7 shows that the poly(ester-carbonate) copolymer compositions notonly have good flow and heat resistance compared to benchmark materialsin the industry, but also have comparable defect on-set temperatures(DOT). The defect on set temperatures of the poly(ester-carbonate)copolymer compositions of the disclosure are within 10 degrees (° C.) ofthe HDT (0.45 MPa) indicating that the adhesion to the metal surface isexcellent and the compositions have low water absorption.

Set forth below are various embodiments of the disclosure, which are notlimiting.

Embodiment 1

A poly(ester-carbonate) copolymer, comprising carbonate units of theformula (1); and ester units of the formula (2) wherein: T is a C₂₋₂₀alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀ arylene; and R¹ and J areeach independently (a) a bisphenol A divalent group, and (b) aphthalimidine divalent group of the formula (3) wherein R^(a) and R^(b)are each independently a C₁₋₁₂ alkyl, C₂₋₁₂ alkenyl, C₃₋₈ cycloalkyl, orC₁₋₁₂ alkoxy, each R³ is independently a C₁₋₆ alkyl, R⁴ is hydrogen,C₁₋₆ alkyl, or phenyl optionally substituted with 1 to 5 C₁₋₆ alkylgroups, preferably wherein R⁴ is hydrogen, methyl, or phenyl, p, q, andj are each independently 0 to 4, provided that a phthalimidine divalentgroup (b) is present in an amount of 40 mol % to 50 mol % based on thetotal moles of the bisphenol A divalent groups and the phthalimidinedivalent group, and the ester units are present in an amount of 40 mol %to 60 mol % based on the sum of the moles of the carbonate units and theester units; and wherein the poly(ester-carbonate) copolymer has aweight average molecular weight of 18,000 Daltons to 24,000 Daltons, asmeasured by gel permeation chromatography, using a crosslinkedstyrene-divinylbenzene column and calibrated to bisphenol Ahomopolycarbonate references; and a sample of the composition has aglass transition temperature of 210° C. to 235° C. as determined bydifferential scanning calorimetry (DSC) as per ASTM D3418 with a 20°C./min heating rate; and a melt viscosity of less than 1050 Pa·s at 644sec-1 and 350° C., determined according to ISO11443.

Embodiment 2

The poly(ester-carbonate) copolymer of Embodiment 1, wherein R¹ and Jare each independently the bisphenol A divalent group or thephthalimidine divalent group; and at least a portion of the J groups arethe phthalimidine divalent group.

Embodiment 3

The poly(ester-carbonate) copolymer of Embodiment 1 or Embodiment 2,wherein the poly(ester-carbonate) copolymer comprises phthalimidinedivalent groups (b) and the mol % of the phthalimidine divalent groups,the mol % of the ester units, and the weight average molecular weight ofthe poly(ester-carbonate) copolymer are selected according to thefollowing formula: Tg=127.1+(0.94375×Mol % PPP)+(0.3875×Mol %Ester)+(0.00164968×Mw).

Embodiment 4

The poly(ester-carbonate) copolymer of any one of Embodiments 1 to 3,wherein the copolymer comprises phthalimidine-carbonate-phthalimidinelinkages (20) in an amount of greater than 15 mol % and less than 50 mol% based on the total moles of the carbonate linkages as determined bycarbon 13 nuclear magnetic resonance spectroscopy.

Embodiment 5

The poly(ester-carbonate) copolymer of any one of Embodiments 1 to 4,wherein greater than 20 mol % and less than 35 mol % of the J groups arethe phthalimidine group based on the total moles of the J groups.

Embodiment 6

The poly(ester-carbonate) copolymer of any one of Embodiments 1 to 5,having one or more of the following properties: a shift in meltviscosity of less than 25% at 350° C. over 30 min under a nitrogenatmosphere as measured in a small amplitude oscillatory time sweeprheology at a fixed angular frequency of 10 radians/sec; a glasstransition temperature of 220° C. to 235° C. as determined bydifferential scanning calorimetry (DSC) as per ASTM D3418 with a 20°C./min heating rate; a Vicat B120 of 220 to 225° C., measured accordingto ISO 306; a melt viscosity of less than 1000 Pa·s at 644 sec⁻¹ and350° C., determined according to ISO11443; or a yellowness index of lessthan 18 determined in accordance with ASTM D1925.

Embodiment 7

The poly(ester-carbonate) copolymer of any one or more of Embodiments 1to 6, wherein R¹ and J consist of the bisphenol A divalent group (a) orthe phthalimidine group (b).

Embodiment 8

The poly(ester-carbonate) copolymer of any one or more of Embodiments 1to 7, wherein T is a C₆₋₂₀ divalent aromatic group.

Embodiment 9

The poly(ester-carbonate) copolymer of any one or more of Embodiments 1to 8, wherein T is a divalent isophthaloyl group, a divalentterephthaloyl group, or a combination thereof.

Embodiment 10

The poly(ester-carbonate) copolymer of any one or more of Embodiments 1to 9, wherein p, q, and j are zero, and R⁴ is hydrogen, methyl, orphenyl.

Embodiment 11

A thermoplastic composition comprising the poly(ester-carbonate)copolymer of any one or more of Embodiments 1 to 10.

Embodiment 12

The thermoplastic composition of Embodiment 11 further comprising apolycarbonate homopolymer, preferably a bisphenol A homopolycarbonate, asecond poly(ester-carbonate) different from the poly(ester-carbonate)copolymer, a copolycarbonate, or a combination comprising at least oneof the foregoing.

Embodiment 13

The thermoplastic composition of any one or more of Embodiments 11 to12, wherein the composition has a haze of less than 15% and atransmission greater than 75%, each measured in accordance with ASTMD1003 using the color space CIE1931 (Illuminant C and a 2° observer) ata 3.2 mm thickness.

Embodiment 14

The poly(ester-carbonate) copolymer or the thermoplastic composition ofany one or more of Embodiments 1 to 13, wherein a metalized sample ofthe poly(ester-carbonate) copolymer or the thermoplastic composition hasa defect onset temperature that is within 10 degrees Celsius of the heatdeflection temperature of the poly(ester-carbonate) copolymer or thethermoplastic composition measured flat on a 80×10×4 mm bar with a 64 mmspan at 0.45 MPa according to ISO 75/Bf.

Embodiment 15

The poly(ester-carbonate) copolymer or the thermoplastic composition ofany one or more of Embodiments 1 to 14, wherein a metalized sample ofthe poly(ester-carbonate) copolymer or the thermoplastic composition hasa defect onset temperature of 200 to 220° C.

Embodiment 16

The poly(ester-carbonate) copolymer or the thermoplastic composition ofany one or more of Embodiments 1 to 15, wherein thepoly(ester-carbonate) copolymer or the thermoplastic composition at agiven temperature has a melt viscosity of less than 1050 Pa·s at 644sec⁻¹ and a shift in melt viscosity of less than 25% at the giventemperature over 30 min under a nitrogen atmosphere as measured in asmall amplitude oscillatory time sweep rheology at a fixed angularfrequency of 10 radians/sec.

Embodiment 17

The poly(ester-carbonate) copolymer or the thermoplastic composition ofany one or more of Embodiments 1 to 16, wherein the copolymer or thecomposition has a melt flow rate of 10 to 30 cm³/10 minutes measured at330° C. under a load of 2.16 kg in accordance with ASTM D1238-04.

Embodiment 18

An article comprising the copolymer or composition of any one or more ofEmbodiments 1 to 17, wherein the article is a molded article, athermoformed article, an extruded film, an extruded sheet, one or morelayers of a multi-layer article, a substrate for a coated article, or asubstrate for a metallized article.

Embodiment 19

The article of Embodiment 18, wherein the article is a metallizedarticle comprising the copolymer or composition of any one or more ofEmbodiments 1 to 17, wherein the defect onset temperature of themetallized article is within 10° C. of the heat deflection temperatureof the copolymer or the composition measured flat on a 80×10×4 mm barwith a 64 mm span at 0.45 MPa according to ISO 75/Bf.

Embodiment 20

The article of Embodiment 19, comprising a substrate comprising thecopolymer or composition of any one or more of Embodiments 1-17; and ametal layer disposed on at least one side of the substrate.

Embodiment 21

A method for the manufacture of the poly(ester-carbonate) copolymercomprises: providing a slurry comprising water, a water-immiscibleorganic solvent, a phase transfer catalyst, and bisphenol A; co-feedingto the slurry a solution comprising aqueous NaOH or aqueous KOH, anaromatic dicarboxylic halide of the formula

wherein T is a C₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀arylene, and a dihydroxy compound of the formula

wherein R^(a) and R^(b) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy, each R³ is independently aC₁₋₆ alkyl, R⁴ is hydrogen, C₁₋₆ alkyl, or phenyl optionally substitutedwith 1 to 5 C₁₋₆ alkyl groups, preferably wherein R⁴ is hydrogen,methyl, or phenyl, p, q, and j are each independently 0 to 4; to providea polyester oligomer; and reacting the polyester oligomer with acarbonate source to provide the poly(ester-carbonate).

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. “Or” means “and/or.” Theendpoints of all ranges directed to the same component or property areinclusive and independently combinable. Unless defined otherwise,technical and scientific terms used herein have the same meaning as iscommonly understood by one of skill in the art to which this inventionbelongs. As used herein, a “combination” is inclusive of blends,mixtures, alloys, reaction products, and the like.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group.

As used herein, the term “hydrocarbyl” and “hydrocarbon” refers broadlyto a substituent comprising carbon and hydrogen, optionally with 1 to 3heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, ora combination thereof; “alkyl” refers to a straight or branched chain,saturated monovalent hydrocarbon group; “alkylene” refers to a straightor branched chain, saturated, divalent hydrocarbon group; “alkylidene”refers to a straight or branched chain, saturated divalent hydrocarbongroup, with both valences on a single common carbon atom; “alkenyl”refers to a straight or branched chain monovalent hydrocarbon grouphaving at least two carbons joined by a carbon-carbon double bond;“cycloalkyl” refers to a non-aromatic monovalent monocyclic ormulticylic hydrocarbon group having at least three carbon atoms;“cycloalkylene” refers to a divalent group formed by the removal of twohydrogen atoms from two different carbon atoms on one or more rings of acycloalkyl group; “aryl” refers to an aromatic monovalent groupcontaining only carbon in the aromatic ring or rings; “arylene” refersto an aromatic divalent group containing only carbon in the aromaticring or rings; “alkylaryl” refers to an aryl group that has beensubstituted with an alkyl group as defined above, with 4-methylphenylbeing an exemplary alkylaryl group; “arylalkyl” refers to an alkyl groupthat has been substituted with an aryl group as defined above, withbenzyl being an exemplary arylalkyl group; “acyl” refers to an alkylgroup as defined above with the indicated number of carbon atomsattached through a carbonyl carbon bridge (—C(═O)—); “alkoxy” refers toan alkyl group as defined above with the indicated number of carbonatoms attached through an oxygen bridge (—O—); and “aryloxy” refers toan aryl group as defined above with the indicated number of carbon atomsattached through an oxygen bridge (—O—).

Unless otherwise indicated, each of the foregoing groups can beunsubstituted or substituted, provided that the substitution does notsignificantly adversely affect synthesis, stability, or use of thecompound. The term “substituted” as used herein means that at least onehydrogen on the designated atom or group is replaced with another group,provided that the designated atom's normal valence is not exceeded. Whenthe substituent is oxo (i.e., ═O), then two hydrogens on the atom arereplaced. Combinations of substituents or variables are permissibleprovided that the substitutions do not significantly adversely affectsynthesis or use of the compound. Groups that can be present on asubstituted position include nitro (—NO₂), cyano (—CN), hydroxy (—OH),halogen, thiol (—SH), thiocyano (—SCN), C₂₋₆ alkanoyl (e.g., acyl(H₃CC(═O)—); carboxamido; C₁₋₆ or C₁₋₃ alkyl, cycloalkyl, alkenyl, andalkynyl (including groups having at least one unsaturated linkages andfrom 2 to 8, or 2 to 6 carbon atoms); C₁₋₆ or C₁₋₃ alkoxy; C₁₋₁₀ aryloxysuch as phenoxy; C₁₋₆ alkylthio; C₁₋₆ or C₁₋₃ alkylsulfinyl; C₁₋₆ orC₁₋₃ alkylsulfonyl; aminodi(C₁₋₆ or C₁₋₃)alkyl; C₆₋₁₂ aryl having atleast one aromatic rings (e.g., phenyl, biphenyl, naphthyl, or the like,each ring either substituted or unsubstituted aromatic); C₇₋₁₉ arylalkylhaving 1 to 3 separate or fused rings and from 6 to 18 ring carbonatoms; or arylalkoxy having 1 l to 3 separate or fused rings and from 6to 18 ring carbon atoms.

All references cited herein are incorporated by reference in theirentirety. While typical embodiments have been set forth for the purposeof illustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives can occur to one skilled in the artwithout departing from the spirit and scope herein.

What is claimed is:
 1. A poly(ester-carbonate) copolymer, comprisingcarbonate units of the formula

 and ester units of the formula

wherein: T is a C₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀arylene; and R¹ and J are each independently (a) a bisphenol A divalentgroup of the formula

 and (b) a phthalimidine divalent group of the formula

wherein R^(a) and R^(b) are each independently a C₁₋₁₂ alkyl, C₂₋₁₂alkenyl, C₃₋₈ cycloalkyl, or C₁₋₁₂ alkoxy, each R³ is independently aC₁₋₆ alkyl, R⁴ is hydrogen, C₁₋₆ alkyl, or phenyl optionally substitutedwith 1 to 5 C₁₋₆ alkyl groups, preferably wherein R⁴ is hydrogen,methyl, or phenyl, p, q, and j are each independently 0 to 4, providedthat the phthalimidine group (b) is present in an amount of 40 mol % to50 mol % based on the total moles of the bisphenol A divalent groups (a)and the phthalimidine groups (b); the ester units are present in anamount of 40 mol % to 60 mol % based on the sum of the moles of thecarbonate units and the ester units; the copolymer comprisesphthalimidine-carbonate-phthalimidine linkages in an amount of greaterthan 15 mol % and less than 50 mol % based on the total moles of thecarbonate linkages as determined by carbon 13 nuclear magnetic resonancespectroscopy; and wherein the poly(ester-carbonate) copolymer has aweight average molecular weight of 18,000 Daltons to 24,000 Daltons, asmeasured by gel permeation chromatography, using a crosslinkedstyrene-divinylbenzene column and calibrated to bisphenol Ahomopolycarbonate references, the poly(ester-carbonate) copolymer has ashift in melt viscosity of less than 25% at 350° C. over 30 min under anitrogen atmosphere as measured in a small amplitude oscillatory timesweep rheology at a fixed angular frequency of 10 radians/sec; and ayellowness index of less than 18 determined in accordance with ASTMD1925; and a molded sample of the composition has a glass transitiontemperature of 210° C. to 235° C. as determined by differential scanningcalorimetry (DSC) as per ASTM D3418 with a 20° C./min heating rate; amelt viscosity of less than 1050 Pa·s at 644 sec-1 and 350° C.,determined according to ISO11443.
 2. The poly(ester-carbonate) copolymerof claim 1, wherein R¹ and J are each independently the bisphenol Adivalent group or the phthalimidine divalent group; and at least aportion of the J groups are the phthalimidine divalent group.
 3. Thepoly(ester-carbonate) copolymer of claim 1, wherein thepoly(ester-carbonate) copolymer comprises phthalimidine divalent groups(b) and the mol % of the phthalimidine divalent groups (Mol % PPP), themol % of the ester units (Mol % Ester), and the weight average molecularweight of the poly(ester-carbonate) copolymer (Mw) are selectedaccording to the following formula:Tg=127.1+(0.94375×Mol % PPP)+(0.3875×Mol % Ester)+(0.00164968×Mw). 4.The poly(ester-carbonate) copolymer of claim 1, wherein the copolymercomprises phthalimidine-carbonate-phthalimidine linkages in an amount ofgreater than 15 mol % and less than 40 mol % based on the total moles ofthe carbonate linkages as determined by carbon 13 nuclear magneticresonance spectroscopy.
 5. The poly(ester-carbonate) copolymer of claim1, wherein greater than 20 mol % and less than 35 mol % of the J groupsare the phthalimidine group based on the total moles of the J groups. 6.The poly(ester-carbonate) copolymer of claim 1, having one or more ofthe following properties: a glass transition temperature of 220° C. to235° C. as determined by differential scanning calorimetry (DSC) as perASTM D3418 with a 20° C./min heating rate; a Vicat B120 of 220 to 225°C., measured according to ISO 306; or a melt viscosity of less than 1000Pa·s at 644 sec⁻¹ and 350° C., determined according to ISO11443.
 7. Thepoly(ester-carbonate) copolymer of claim 1, wherein R¹ and J consist ofthe bisphenol A divalent group (a) or the phthalimidine group (b). 8.The poly(ester-carbonate) copolymer of claim 1, wherein T is a C₆₋₂₀divalent aromatic group.
 9. The poly(ester-carbonate) copolymer of claim1, wherein T is a divalent isophthaloyl group, a divalent terephthaloylgroup, or a combination thereof.
 10. The poly(ester-carbonate) copolymerof claim 1, wherein p, q, and j are zero, and R⁴ is hydrogen, methyl, orphenyl.
 11. A thermoplastic composition comprising thepoly(ester-carbonate) copolymer of claim
 1. 12. The thermoplasticcomposition of claim 11 further comprising a polycarbonate homopolymer,a second poly(ester-carbonate) different from the poly(ester-carbonate)copolymer, a copolycarbonate, or a combination comprising at least oneof the foregoing.
 13. The thermoplastic composition of claim 11, whereinthe composition has a haze of less than 15% and a transmission greaterthan 75%, each measured in accordance with ASTM D1003 using the colorspace CIE1931 (Illuminant C and a 2° observer) at a 3.2 mm thickness.14. The poly(ester-carbonate) copolymer of claim 1, wherein a metalizedsample of the poly(ester-carbonate) copolymer has a defect onsettemperature that is within 10 degrees Celsius of the heat deflectiontemperature of the poly(ester-carbonate) copolymer measured flat on a80×10×4 mm bar with a 64 mm span at 0.45 MPa according to ISO 75/Bf. 15.The poly(ester-carbonate) copolymer of claim 1, wherein a metalizedsample of the poly(ester-carbonate) copolymer has a defect onsettemperature of 200 to 220° C.
 16. The poly(ester-carbonate) copolymer ofclaim 1, wherein the poly(ester-carbonate) copolymer at a giventemperature has a melt viscosity of less than 1050 Pa·s at 644 sec⁻¹ anda shift in melt viscosity of less than 25% at the given temperature over30 min under a nitrogen atmosphere as measured in a small amplitudeoscillatory time sweep rheology at a fixed angular frequency of 10radians/sec.
 17. The poly(ester-carbonate) copolymer of claim 1, whereinthe copolymer has a melt flow rate of 10 to 30 cm³/10 minutes measuredat 330° C. under a load of 2.16 kg in accordance with ASTM D1238-04. 18.An article comprising the copolymer of claim 1, wherein the article is amolded article, a thermoformed article, an extruded film, an extrudedsheet, one or more layers of a multi-layer article, a substrate for acoated article, or a substrate for a metallized article.
 19. The articleof claim 18, wherein the article is a metallized article comprising thecopolymer of claim 1, wherein the defect onset temperature of themetallized article is within 10° C. of the heat deflection temperatureof the copolymer measured flat on a 80×10×4 mm bar with a 64 mm span at0.45 MPa according to ISO 75/Bf.
 20. The article of claim 19, comprisinga substrate comprising the copolymer of claim 1; and a metal layerdisposed on at least one side of the substrate.
 21. A method for themanufacture of the poly(ester-carbonate) copolymer of claim 1, themethod comprising: providing a slurry comprising water, awater-immiscible organic solvent, a phase transfer catalyst, andbisphenol A; concurrently but separately adding to the slurry (1) anaromatic dicarboxylic halide of the formula

and (2) a solution comprising aqueous NaOH or aqueous KOH and adihydroxy compound of the formula

to provide a polyester oligomer; and reacting the polyester oligomerwith a carbonate source to provide the poly(ester-carbonate).